Hi @bhindhiya
Yes, it's possible to use the 64-pin SAMD21.
Provided you use the same 256k flash, 32k RAM version, in other words the SAMD21J18A, as well as an external 32.768kHz crystal, then the chip can be programmed with the standard Arduino Zero bootloader and even run Arduino sketches that use that same (port) pins as the 48-pin, SAMD21G18A.
However, to benefit from the device's additional pins (without having to accessing them directly using the microcontroller's registers), you'll need either follow @in0 advice and use an existing supported board, which is by far the easiest option, or alternatively modify the Arduino SAMD21 core file called "variant.cpp" and append them as new entries to the pin list.
Here's the additional lines that I added to the pin description array in the "variant.cpp" file for my custom SAMD21J18A board:
// SAMD21J18A Pins...
// 44..47 - Analog pins
{ PORTB, 4, PIO_ANALOG, 0, ADC_Channel12, NOT_ON_PWM, NOT_ON_TIMER, EXTERNAL_INT_4 }, // ADC/AIN[12]
{ PORTB, 5, PIO_ANALOG, 0, ADC_Channel13, NOT_ON_PWM, NOT_ON_TIMER, EXTERNAL_INT_5 }, // ADC/AIN[13]
{ PORTB, 6, PIO_ANALOG, 0, ADC_Channel14, NOT_ON_PWM, NOT_ON_TIMER, EXTERNAL_INT_6 }, // ADC/AIN[14]
{ PORTB, 7, PIO_ANALOG, 0, ADC_Channel15, NOT_ON_PWM, NOT_ON_TIMER, EXTERNAL_INT_7 }, // ADC/AIN[15]
// 48..51 - Digital pins
{ PORTB, 12, PIO_DIGITAL, (PIN_ATTR_DIGITAL), No_ADC_Channel, NOT_ON_PWM, NOT_ON_TIMER, EXTERNAL_INT_12 },
{ PORTB, 13, PIO_DIGITAL, (PIN_ATTR_DIGITAL), No_ADC_Channel, NOT_ON_PWM, NOT_ON_TIMER, EXTERNAL_INT_13 },
{ PORTB, 14, PIO_DIGITAL, (PIN_ATTR_DIGITAL), No_ADC_Channel, NOT_ON_PWM, NOT_ON_TIMER, EXTERNAL_INT_14 },
{ PORTB, 15, PIO_DIGITAL, (PIN_ATTR_DIGITAL), No_ADC_Channel, NOT_ON_PWM, NOT_ON_TIMER, EXTERNAL_INT_15 },
// 52..53 - SERCOM/UART (Serial1)
{ PORTB, 16, PIO_SERCOM, (PIN_ATTR_DIGITAL), No_ADC_Channel, NOT_ON_PWM, NOT_ON_TIMER, EXTERNAL_INT_0 }, // TX: SERCOM5/PAD[0]
{ PORTB, 17, PIO_SERCOM, (PIN_ATTR_DIGITAL), No_ADC_Channel, NOT_ON_PWM, NOT_ON_TIMER, EXTERNAL_INT_1 }, // RX: SERCOM5/PAD[1]
// 54..55 - Digital pins
{ PORTB, 30, PIO_DIGITAL, (PIN_ATTR_DIGITAL), No_ADC_Channel, NOT_ON_PWM, NOT_ON_TIMER, EXTERNAL_INT_14 },
{ PORTB, 31, PIO_DIGITAL, (PIN_ATTR_DIGITAL), No_ADC_Channel, NOT_ON_PWM, NOT_ON_TIMER, EXTERNAL_INT_15 },
// 56..57 - Analog pins
{ PORTB, 0, PIO_ANALOG, 0, ADC_Channel8, NOT_ON_PWM, NOT_ON_TIMER, EXTERNAL_INT_0 }, // ADC/AIN[8]
{ PORTB, 1, PIO_ANALOG, 0, ADC_Channel9, NOT_ON_PWM, NOT_ON_TIMER, EXTERNAL_INT_1 }, // ADC/AIN[9]
// 58..59 - SERCOM/UART (Serial2)
{ PORTA, 12, PIO_SERCOM, (PIN_ATTR_DIGITAL), No_ADC_Channel, NOT_ON_PWM, NOT_ON_TIMER, EXTERNAL_INT_12 }, // TX: SERCOM2/PAD[0]
{ PORTA, 13, PIO_SERCOM, (PIN_ATTR_DIGITAL), No_ADC_Channel, NOT_ON_PWM, NOT_ON_TIMER, EXTERNAL_INT_13 }, // RX: SERCOM2/PAD[1]